Manufacture of cellulose products



Ju ne 29 1926. 1,590,603

E. TAYLOR MANUFACTURE OF GELLULOSE PRODUCTS Filed June 17. 1924 I am Ami/1% ATTORNEYS paste is. 29, 1 9 26.

1,590,603 PATENT; OFFICE.

; nnwm TAYLOR, or Bnooxmm, w s; Assreuon Tennyson nnom'ronms,

' me, or New YORK, 1;. Y., A. CORPORATION or new YORK.

menurac'runn or. cnt'LUL'osE rnonucrs.

Application filed June 17,

My invention relates to improvements inv the manuiactureof cellulose products and is more articularly illustrated and-described hereina er in its a plication to the production of cellulose s and similar articles, the'apparatus' described having particular reference to films or ribbons made from p organic material such as cellulose dissolved 1 in'solvents contaming a metal. such as cupro- 10 ammonia solution or zinc chloride and from 1 which solutions the organic material isdeposited in, a solid state upon an anode and the metallic solution-element deposited on 'a cathode by means of a suitable electrical current. 1 v In carrying out the invention in one form, I pass a'. metallic belt through an electrical field in as'uitable bath the belt constituting the anode upon which the organic material is deposited while the metallic solvent constituent is deposited upon a suitable cathode or cathodes. By this arrangement a con-' tinuous film may be roduced and its thickness may be governs according to the thickness or density of the solution. Where the belt serves as the anode, the organic material should remainin contact therewith until the last traces of metal have been removed from ,it. .In the apparatus hereinafter described, a suitable belt, not necessarily of "greatlength and preferably of'platinum, or platinum plated is'caused to pass continuously through a containerfilled with say for instance, cellulose dissolved in-cupro ammonia.

By-suitable connections this belt which forms the anode carries an electrical current which passes through'itand' through the cellulose solution or bath to the suitably located .cathodes upon which the metallic constituent 40 is deposited. :In a preferred form oi apparatus, both belt and cellulo'se'solution are moved through the tank or container in the same direct on. The electrical current causes the deposition of cellulose upon the belt in a-gradually' increasing thickness from Y the point of its first-immersion and the cellulose solution is correspondingly reduced in cellulose content and a proportionate amount of solution metal. is deposited on the cathodes from which it must be evident that the thickness and density of the deposited film depends u on several f actors-each of which may be rought fully and conveniently under control of the .operator, i. e., the speed I of the beltythe time oi contact between the thereby doubling the output per square foot 1924. Serial No. 720,524.

belt and cellulose solution, rate of flow of cellulose solution relative to speed of belt with a consequent Variation, in strength of the cellulose solution at any point in the tank, and the amount of current passing durin any interval of time, etc. In practice, t ese factors may be so regulated that as the belt emerges 'from the tank it is coated with a predetermined thickness of'cellulose which may then be stripped from the belt in a conditlon'permitting it to be subjected to further operations, or if desired, before stripping it can be scraped to remove surplus adhering material. It may then be passed through a second electrolytic bath,

.washed, and passed. on for further treatment. The cellulose solution reduced in strength by the amount of cellulose de- 'It materially reduces the length and cost of the belt v(important in some cases where platinum is used) and its subsequent upkeep.- The arrangement of thejapparatus hereinafter described allows forcoatmg the belton both sides where this is desired,

-00- ofone side of belt surface, or where. a wheel is employed for casting or flowing the material as. in other well known processes. Numerous other advantages willbe apparent hereinafter. I

In the accompanying drawing forming -a part of this specification -I have illustrated in vertical section one form of apparatus suitable for carrying out the inventlon. Re-

ferring to the drawing, 1 indicates a closed 1 tank provided with a supply pipe 2 and an outlet 3 provided with a suitable control valve '4. The pipe 3 enters the side of the tank 5 which may be providedwith a series of partitions, or walls 6,. dividing the tank several divisions 7,' 8, 9 and. 10,. as

shown, so that liquid flowing from the pipe 1 3'must cpass successively through these chamhere an finally out of'the upper part ofthe division or compartment 7 of the chamber v 3. ,wardly infythe tank 10 pmtically aS"'far' a.'S

by way-of the overflow pipe 11 which may' vbe provided with a suitable valve such as I platinum-plated or preferably'o'f pure plattnum, is suitably driven-upon the overhead rollers 17, enters the tank passing through the centres of the compartme11ts--7 to inclusi-veaas shown, being guided andposi-- tionedby the rollers 18' in said tank-,5) and i i indicates acent -both sidesof theybet asit emerges 2.5 from the tank-5 and serves to remove any the small rollers 19. The upper -peripheries of the rollers 18 practically contact withthe lower extremities of-the partitions 6 but a suitable space is left between the lower sides -or peripheries of the rollers and the bottom of the-tank 5 as shown, so that the liquid may.pass?freely from one oo'm'partmen't'to another'from below} the lower rollers 18 and over the,t.(:1ps-of1fthe upperrollers 19. 20

ustable soft-ed ed scrapers adadhering material from the films of cellulose deposited upon the. belt.

21"" di i at" a suitable bus-bar or electrip-lcal-raileonnectedby the wire 22. to the ne tive sou'reeof electricity 23, and from t s busgbariare suspended a series of copper or othermet-allie plates 21 so that'at leasttwo of them "arejin' of -the; compartments tant from thebe 7 to 10 inclusiveiparallelftoi and eqiiall dis t'f-16 and-extending own the belt 1e;:.-i j The trolley or rolling contact 25 is -connected by a wire 25' to the positive terminal 27"of the same electrical source. Any suitable motive power may be applied was drive pulley 17 and a pair of brushes, scrapers orrother suitable apparatustmay be employed as indica edat'26 for cleanin the. belt after the has been stripped erefi In operation, the tank 5' is filledwith any desired cellulose solution, such cupro-v' ammoma, mckelnammoma, zmcchloridef etc;

Having-filled the tank? to the level- '0 "the outlet. pipe 11, the tank 1 is now filled with the same kind of. solution, the' zcontrol valve ,4 isopenedandiaflow ofjliquid is GStll lishe'cl through the tank 5,'out1et pipe 11,-and' into thejdilute "solutiontank 13.; The belt 16 is now started in thedirection qindicated H v "adapted to remove electrolytically. any re-.-

by the arrow. and :preferably' in av direction parallel' with'the flow of the "solu tion' andthe" electric current. isturned. on.- jGellulosewill immediately begin to depositon each..side of the belt, becoming thicker and thicker as the belt progressesthrough; the tank'5; the cellulose solution vbecoming.

,weaker in like proportion, from the point of l immersion "of the beltin the first compartq .ment to thepoint of its leaving in the last cook 14 and a vent.

andthe u I iyvh'ich take it'out of the path .of the returning belt 16 as shown, both films enterin the may compartment; It will be apparent that any variation in the amount of'current "passed,

the speed of the belt through the solution,

or the speed of the solution through the tank, will have acorresponding effect on the thickness or quality of the cellulose deposited on the belt andth'at these factors maybe kept under the control of the operator by any well knownmeans. It may be preferable to run the belt rather slowly and to run thesolution slightly slower than the belt inorder to remove the, largest practical amount of cellulose from it before permitting it to flow to the dilute solution in the 13. It isunnecessaryfhowever to remove all-of the cellulose from the solution and it is preferable tokeepthe solution at a a more or less uniform condition-and to 're-' generate or replenish it either by constant lIlflOW of new solution and outflow of partly exhausted'solution' or by gradual periodic replenishment as may be found preferable according to the particular uses and type of apparatus employed.

thickness of cellulose on both faces, and after After the belt 16 has received the desired the soft-edtged scrapers 20 have removed the surplus a thus formed, and have removed or wiped off adhering solution, all of which returns to the tank 5- the belt nowpasses between, the hard-edged 7 separate the film 29-30 'from-thebelt 16, the film .29 assing over'the roller 31,. directly, 30passing over the rollers 32-33 nexttankM at 35 as shown. This arik 34 hering material from the filnr scrapers or strippers, 28 which 'is-fitted wi'th a suitable outlet valve 36 and i a series of'guiderollers 37 38. The'films pass 'under and over these'rolle'rs traversing the liquid in the tank 34' vertically several times, a slight tension being placed upon thetive "electrical terminal 42,; and '43. are the lms by'means ofa driven roller '38; placed in the outer'wall 39. $0 indicates a suitable 'bus-car connected by the wire 41 to the negacathodes suspendodftherefrom."i44i are the 47. The tanks 5 '34 are-covered by a comby way-10f the-outlet 49.

stituent'; which may-adhere tdcior begeonsolution may -be a dilute acid.- such as nitric anodes suspended fr'om-thelbus-bar45 con- ,nect'ed byawire 16 to ,the positive terminal,

' mon hood f8'lfor;collectingthe vapors-which" be :draw'n off by suction -and recovered tracesjof the metallic s nata con-g metallic acid, For some purposes, s'uchfasfilm making,..itis preferable to employ a solution of ammonium nitrate as the ultimate product of th'issalt under. electrolysis is off through-the vent pipe'4-9 and recovered with the-ammonia released from the tank '5 when cupro or nickel ammonia solutions I in a'- suitable condition of cellulose are employed. The arrangement of anodes and cathodes is such that current passing from one to the other must pass not only through the solution but through the'films 28-30 also.

The electrolyte in the tank stantially free of the dissolved organic .material or its solution, the film will be greatly purified therein. During treatment and I passage through the tank 34 the last trace of metal is removed from'the film which ow passes over the roll 38 to a wash tan 50. This'wash tank is provided with an outlet 51 and valve, 52 therefor and with an inlet pipe 53 and valve 54 therefor by means of which a constant flow of liquid is maintained through the tank thereby removing all traces of ammonia or other gases and foreign matter. From the tank 50, the films which pass over the rollers 55 may now be wound upon the reels 56-57 under slight tension,'which reels maybe removed from time to time as complete The film thus made is pure cellulose, quite tough and elastic and of a white translucent appearance owing to its-content of water. It is however for further desired operations- The dilute cellulose solution flowing into the tank13is drawn oil from time to time, regenerated and returned to the tank 1, for passage through the tank 5. In the-case-of a cupro ammonia solution, for instance, the liquid inthe tank 13'contains cellulose, copper, ammonia and an undue amount of water. This solution may be first cooled, then saturated with ammonia gas after which hydrated cufptrlic-oxide may be added to saturation and ally any-desired grade of cel lulose also'to saturation. The solution may thellltbe filtered, andif desired returned to tan 1 may now be passed over a series of hot rolls. if desired and dried: thus made can be produced; with glass-like transparenc and of high tensile "strength. It can be at? to a variet of purposes. It may be cut or .oth'e rwiseormed .in' grains nitrated with a mixture of nitric "and" sulphuric acids,

washed, stabilized and dried and an excellent smokeless powder, produced without the use still sli'ghtly moist with-:ahot solution of nitric acidof about concentration, a material, is obtained rather low in nitrogen content but- StiILdecidedly solublefn .volatile-. solvents and of value asawaterproof-r'coatforlv mish and p 34' being subleaves the roller 55.

the ammonia and copper used having 'been' obtained largely by recove from the I reat detail and wi of a volatile solvent.- By treatment while For the production of photographic films,

a preferred method of treatment is to pro-,

tect one side of the film by means-of a coata removed (when used) and the film is passed 8 through an electric field b'etweenelectrodes immersed in a dilute alkaline solution by which means the last traces of acid are readily removed or decomposed. The film is again washed in hot running water and may be dried on hotrolls. It is now passed" through a volatile solvent such as acetone or amyl acetate, the non-nitrated side bein pro:

tected by a drum and the nitratedsi e 'gelatinated to the full depth of nitration. The 9 film is now drawn through a dryingchamher and the volatile solvent removed; At

this stage the product consists of a tough cellulose-like, waterproof backing gradually merging into a non-nitrated water-absorbing 9. facing. The facing is now impre 'nated with any desired light-sensitive- -sa ts,- passed through boiling water to improve the sensitiveness if desired and finally dried; All. ofthe above operations are continuous, and where space .is available the reels 56-4)! may be diSpe'nsed, with and-the above operations carried 011 immediately afterthe film In case-it is desired to produce an elastic 1 or flexible condition such as may be required for artificial leather, the film after leaving the roll 55 on the wash tank 50 may be le through a solution of glycerine' and water, say about thirt per cent (-30%).glycer'ine for about a hal hour preferably maintained at a temperature of say about 220 Fahrenheit. This forms a glycerine of-cellulose which leaves,the non-hydroscopic under atmospheric conditions. a i While the'improvements are .espec1ally'ap-- ;.plicable to the treatment "of fce'llulosio ma-w ep terials,' they may beusefully applied to other .organic materials, such 'forexample as silk" 'which may be dissolved in anickel ammonia solution to form the electrolyte;

While -I have described my improvements I respect to preferred em entsthereofi: do, not' desi're to be limited to such details orembodinients, since manychanges and modifications lmay be niadei and the invention embodied in widely.

diflerent'forms without departingfrom the spirit and scope thereof in its broader aspects; hence I desii'etocover all modifica- 1 i generaldirection as the carrier but independently thereof, whereby organic material is electrolytically deposited on the carrier from the solution as the two pass through the cell. c p

2. The method which consists in passing an anode gradually through an electrolytic cell and causing a solution of cellulose to travel through. the cell in the same general direction as-the anode but independentlyv thereof, whereby cellulose is deposited electrolytically on the -anode as the two;,lpass through the cell.

. 3. The method which consists in .Pa Si g an electrode. through a atank'having therein;

an electrolytic bath containing or anic matter in solution while causing theath to be replenished with organic material.

4. The method which consists in gradually passing anelectrode through a tank having therein an-electrolytic bath containing cellulose in solution, depositing cellulose on the electrode, while replenishing the bath with fresh cellulosic material.

5. The method which consists in passing a metallic anode carrier through a tank containing an electrolytic bath solution of cellulose whereby cellulose is electrolytically deposited onthe carrier, while withdrawing expended electrolyte from one part. of the bath and introducing fresh cellulose electrolyte to the carrier. v

6. In an apparatus of the class described, an electrolyticcell, a movable electrode traveling through the cell, means for introbath independently of the du'cing electrolyte at one part of the cell and means for withdrawing expended electrolyte at another part of the cell.

7 In an apparatus of the class described, an electrolytic cell, a movable'anode carrier traveling through the cell, means for introducing electrolyte to the part of the cell where the carrier enters the cell, and means for Withdrawing expended electrolyte from the part of the cell where the carrier leavesthe cell.

8. In an apparatus of the class described, an electrolytic cell, a movable electrode traveling'through the cell, means for introducing electrolyte at one part of the cell and means for withdrawing expended electrolyte at' another part of the cell anda cathode on 'both sides ofthe movable elec- Jtrodeinthe cell.

. Y 9, an apparatus of theclassdescribed,

.ducing electrolyte at one part of the cell metallic belt, and cathodes on both sides of said belt in the cell.

10. In an apparatus of'the class described as electrolytic cell, a movable carrier travela .ing through the cell on which material is electrodeposited in the cell, means for introindependently of the carrier, and means for withdrawing expended electrolyte at another part of the cell independently of the carrier.

11. The method which consists in passing an. electrode carrier through an electrolytic ",cell containing a solution of organic mate- Llrial whereby organic material is deposited "eleatrjolytically on the carrier, and then electruly gg theiorganic material in an elec- 'e ubstantiallyv free from said organic material dissolved therein. 7 g

.12. The method which consists-in passing an electrode through an electrolytic bath' containing'organic matter in-solution,where- 9 by organic material is deposited electrolyt ica lly on the carrier while causing the cell.

to be replenished with the organic materiahi and thenelectrolyzing the organic material in an electrolyte substantiall free from said organic material dissolve therein.

13. The method whichconsists in passing a carrier continuously through a tank containing anelectrolyte with organic material therein, and depositing organic materialelectrolytically from the solution onto the carrier as it passes through the tank.

14. The method which consists inpassing an anode carrier through an electrolytic cell containing a cellulose solution whereby cellulose is deposited electrolytically on the carrier as it passes, through the cell, and then treating the cellulose electrolytically in an electrolyte substantially free from dissolved cellulose.

15. The method which consists in passing an anode carrier through anelectrolytic cell containing a cellulose solution whereby cellulose is deposited electrolytically on the carrier as it passes through the cell, and then stripping the cellulose from the car rier and assing it between electrodes in an electrolytic cell, the electrolyte in which is substantially free from dissolved cellulose. 16. Inan apparatus of the class described, an electrolytic cell, a, movable anode car-- rier traveling through the cell, means .for-

introducing electrolyte to the art of the I cell where the carrier enters t e cell and independently of the carrier, and 'meansfor withdrawing expended electrolyte from the part of the cell where the carrier leaves the cell, means for stripping ofi the material deposited on the carrier, a second electrolytic cell and means for conveying said material between the electrodes of said second cell.

17. In an apparatus of the class described, an electrolytic cell, a movable electrode. carrier traveling through the electrolyte in the cell, means for stripping ofi the material deposited on the carrier, a second electrolytic cell and means for conveying said matefial between the electrodes of said second ce 18. The method which consists in pass-' ing an anode carrier through an electrolytic cell containing a solution of cellulosic material with a. metal compound solvent, whereby cellulose is deposited on the anode carrier and the metal 1s deposited on the cathode of the cell, while the weakened soluelectrolysis is proceeding.

into the cell independently of the carrier.

19. The method of treating cellulosic ma terial which consists in providing an electrolytic cell with the cellulosic material in solution in the-electrolyte therein and sub-' jecting the solution to electrolysis in the cell and adding fresh solution of the cellulosic material while the electrolysis is proceeding.

20. The method which consists in providmg an electrolytic cell with cellulosic material in solution in the electrolyte therein, which material is deposited electrolytically on one of the'electrodes of the cell, and adding fresh cellulosic material to be electrolyzed, to the electrolyte in the cell While In testimony whereof I have signed my name to this specification.

EDWIN TAYLOR. 

